Metallocene Supported Catalyst Composition and a Process for the Preparation of Polyolefin Using the Same

ABSTRACT

The invention relates to a metallocene supported catalyst composition and a process for the preparation of polyolefin using the same. A metallocene supported catalyst composition according to the invention is prepared by bringing a compound of a group IV transition metal into contact with an inorganic or organic porous carrier treated with an ionic compound. Advantages of a metallocene supported catalyst composition of the invention include an increase in the catalyst activity during polymerization of slurry and an olefin compound in the vapor phase even at a low content of metallocene metal components within the carrier, and an improvement in solving process problems such as fouling, sheeting, plugging or the like.

TECHNICAL FIELD

The present invention relates to a metallocene supported catalystcomposition, a process for the preparation of olefin polymer using thesame, and an olefin polymer being prepared.

BACKGROUND ART

An olefin polymerization catalyst may be classified as a Ziegler-Nattaheterogeneous catalyst and a metallocene of single-site catalyst, and ametallocene according to the present invention has been developed forproducing various polyolefin products since it was reported by Kaminskiat 1980. The metallocene catalyst is composed of the combination of maincatalyst having a transition metal compound as a principle ingredientwith co-catalyst having aluminum or boron as a principle ingredient. Themetallocene catalyst has the very narrow and homogeneous molecularweight distribution and the chemical compositional distribution of apolyolefin being produced as homogeneous single-site catalyst, and ispossible to freely control the tacticity, the comonomer response, thehydrogen response as the ligand structure of the metallocene catalyst,and to largely improve the related physical property of the polyolefincompared to the Ziegler-Natta catalyst.

In order to apply the metallocene catalyst to slurry or vapor phaseolefin polymerization process, an immobilization is necessarily needed.The reason is that a fatal process problems such as an agglomerate, afouling, a sheeting, a plugging phenomenon or the like of the producedpolymer in case of incorporating the homogeneous metallocene catalyst tothe vapor phase polymerization process are encountered, the shape of theproduced polyolefin polymer particle is very irregular and the apparentdensity is low so that the production of the product is impossible.

In order to solve those several problems, the study on theimmobilization was proceeded, a polymerization method of the polyolefinincluding supporting the metallocene alone or metallocene andco-catalyst to several porous inorganics or organics such as silica,alumina, magnesium dichloride and the like to prepare the metallocenesupported catalyst, and applying them to the slurry or vapor phasepolymerization process.

The conventional metallocene catalyst supporting method includes forexample, the method for supporting the metallocene after treating byadding an aluminum compound, that is, trimethylaluminum,triethylaluminum and the like to the unplasticized silica (U.S. Pat. No.4,937,217, No. 4912075 and No. 4935397), the method for preparing themetallocene supported catalyst by adding the metallocene aftersurface-treating the plasticized silica by methylaluminoxane orsurface-treating the silica containing water by alkylaluminum (U.S. Pat.No. 4,808,561, No. 4912075 and No. 4904631), etc. In addition, themethod for synthesizing the metallocene supported catalyst by addingmetallocene after surface-treating the silica by using the boron-basedorganometallic material instead of the aluminum organometallic compound(U.S. Pat. No. 6,087,293), the method for preparing the metallocenesupported catalyst by surface-treating of the silica by using theorganic compound instead of organometallic compound of aluminum orboron-based and contacting them with metallocene (U.S. Pat. No.5,643,847 and No. 5972823) are known, the method for attaching themetallocene catalyst to the silica surface by forming thecovalent-bonding through the chemical reaction (Korean PatentApplication No. 10-1999-0023575 and Korean Patent No. 10-0536181) areknown.

However, in case of preparing the metallocene supported catalyst by theabove-mentioned methods, there is disadvantages that the catalystcomponent doesn't homogeneously supported in the pore, the time requiredfor preparing the catalyst is long, and the activity of the catalyst islow. In addition, the problems such as the deactivation and the hot spotin the reactor may be caused because alluminoxane is not homogeneouslyexisted in the pore. The polymerized polymer particle is able to causethe fouling or plugging phenomenon by dissolving out the catalystcomponent in the metallocene supported catalyst in the slurrypolymerization process. The method for preparing the metallocenesupported catalyst through the chemical bonding that was alreadydeveloped to solve the above-mentioned catalyst elution problem havedisadvantages that the cost for preparing catalyst is high and theactivity of the prepared catalyst is low due to the method for preparingthrough several stages.

DISCLOSURE Technical Problem

An object of the present invention is to provide the metallocenesupported catalyst requiring to the olefin polymerization bysurface-treating the carrier surface of the inorganics and organics byusing the ionic compound, and supporting the metallocene compound andthe needed co-catalyst, etc. on the surface of the ionic compound,further to provide the method for producing the various polyolefinproducts showing the high-activity and the process driving stability inthe slurry or vapor phase olefin polymerization including the singlereactor or multiple reactor, and the metallocene supporting catalystincluding an increase in the catalyst activity during polymerization ofthe slurry and vapor phase olefin compound even at low content ofmetallocene metal components within the carrier, and an improvement insolving process problems such as fouling, sheeting, plugging, or thelike.

Technical Solution

To achieve the object of the present invention, the present inventionprovides a metallocene supported catalyst composition by treating thesurface of an inorganic or organic porous carrier and the surface on thepore with an ionic compound paring cation and anion, and contacting themetallocene catalyst and alkylaluminoxan or boron compound-basedco-catalyst among the aliphatic carbohydrate with the above, and themethod for preparing an olefin polymer by polymerizing the olefinmonomer or olefin-based and the olefin comonomer thereof by using themetallocene supported catalyst composition.

Hereinafter, the characteristics of the present invention will bedescribed in detail.

The metallocene supported catalyst composition for polymerizing anolefin according to the present invention is characterized in that it isprepared by supporting the Group IV transition metal compoundrepresented by the following Chemical Formula 1 to an inorganic ororganic porous carrier being treated by the ionic compound:

Cp′L¹ML² _(n)  [Chemical Formula 1]

where,

M is a Group IV transition metal of the Periodic Table of the elements;

Cp′ is the fused ring including the cyclopentadiene or cyclopentadienylring being able to η⁵-bond with central metal;

L¹ is the fused ring including cyclopentadiene, cyclopentadienyl ring oran anionic ligand including (C1-C20) hydrocarbon substituent and O, N orP atom;

L² is halogen atom, (C1-020) alkyl group, (C6-C30) aryl (C1-C20) alkylgroup, (C3-C20) cycloalkyl group, (C1-C20) alkoxy group, (C6-C30)aryloxy group, (C6-C30) aryl group, (C1-C20) alkyl substituted or(C6-C30) aryl substituted sillyl group, (C1-C20) alkyl substituted or(C6-C30) aryl substituted amino group, (C1-C20) alkyl substituted or(C6-C20) aryl substituted siloxy group, and (C1-C20) alkyl substitutedor (C6-C30) aryl substituted phosphine group;

n is an integer of 1 or 2;

Cp′ and L¹ may not be connected each other, or may be connected to asilicon or (C1-C4) alkenylene bond;

the cyclopentadienyl ring or cyclopentadienyl fused ring of the Cp′ andL¹ may be further substituted with (C1-C20) alkyl group, (C6-C30) arylgroup, (C2-C20) alkenyl group or (C6-C30) aryl (C1-C20) alkyl group.

In other words, a carrier that the metallocene catalyst represented bythe Chemical Formula 1 in the metallocene supported catalyst compositionis supported, is an adoption of the porous inorganic or organic materialcarrier having the hydroxy group on the surface of the carrier pore, thecarrier having the hydroxy group on the surface of the carrier pore maybe obtained by physicochemically surface-treating the surface inside andoutside the carrier pore by treating for sufficiently wetting with anionic compound having liquid or solid phase in the inorganic or organicporous carrier at room temperature and paring a cation and anion.

The ionic compound useful in the present invention includes all of thecommercialized ionic compounds, and further new ionic compound may beused through the synthesis according to the metallocene catalyst, thestructure of the co-catalyst and the type of the carrier. Thecharacteristic of the commercialized or synthesizable ionic compound isthat the vapor pressure of the ionic compound is close to 0, and ispolar to liquid or solid phase, the polarity is depends on the type ofan anion material, various type of the ionic material including fromvery weak polarity to very strong polarity may be adopted, and also itmay be used in the present invention as ionic compounds not containingthe impurity if the molecular structure of the metallocene catalyst isnot changed to be inert. The metallocene supported catalyst compositionaccording to the present invention is exemplified by forming the ioniccompound paring a cation (X⁺) and anion (Y⁻) such as the compoundrepresented following the Chemical Formula 2, but the ionic compounddoes not limited thereto.

X⁺Y⁻  [Chemical Formula 2]

where,

X⁺ is imidazolium ion, pyridium ion, ammonium ion, phosphonium ion,sulfonium ion, pyrazolium ion or pyrrolidium ion;

Y⁻ is BF₄ ⁻, PF₆ ⁻, AlCl₄ ⁻, halogen⁻, CH₃CO₂ ⁻, CH₃CO₂ ⁻, CH₃SO₄ ⁻,CF₃SO₃ ⁻, (CF₃SO₂)N⁻, NO₃ ⁻, SbF₆ ⁻, Sb₂F11⁻, MePhSO₃ ⁻, (CF₃SO₂)₂N⁻,(CF₃SO₂)₃C⁻ or (OR)₂PO₂ ⁻.

In the Chemical Formula 2, the cation (X⁺) is exemplified by followingTable 1.

TABLE 1 Cation Structure (X⁺)

Structure Name imidazolium ion pyridinium ion ammonium ion phophoniumion sulfonium ion pyrazolium ion pyrrolidium ion

In the above-mentioned table, R, R₁ to R₃ are selected from the alkylgroups that the functional group such as an alkyl group or —OH, —SO₃H,—COOH, amine, silane, alkoxy, and the like is attached.

In the above-mentioned Chemical Formula 2, the anion (Y⁻) is exemplifiedby following Table 2.

TABLE 2 Anion(Y⁻) Anion Name Anion(Y⁻) Anion Name BF₄ ⁻tetrafluoroborate (CF₃SO₂)N⁻ bis[(trifluoro- methyl)sulfonyl PF₆ ⁻hexafluorophsphate NO₃ ⁻ nitrate AlCl₄ ⁻ aluminium chloride SbF₆ ⁻hexafluoro- animonate Cl⁻, X⁻ chloride, halogen Sb₂F11⁻ CH₃CO₂ ⁻ acetateMePhSO₃ ⁻ tosylate CF₃CO₂ ⁻ trifluoroacetate (CF₃SO₂)₂N⁻bis(trifluorometh- ylsulfonyl)imide CH₃SO₄ ⁻ methylsulfate (CF₃SO₂)₃C⁻tris(trifluorometh- ylsulfonyl)methide CF₃SO₃ ⁻ trifluoromethyl-(OR)₂PO₂ ⁻ dialkyl phosphate sulfate

Also, the ionic compound that may be used in the present inventionincludes for example, 1-butyl-3-methylimidazolium chloride,1-butyl-3-methylimidazolium dibutylphosphate,1-butyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazoliumhexafluoroantimonate, 1-butyl-3-methylimidazolium hexafluorophosphate,1-butyl-3-methylimidazolium hydrogencarbonate,1-butyl-3-methylimidazolium hydrogensulfate, 1-butyl-3-methylimidazoliummethylsulfate, 1-butyl-3-methylimidazolium tetrachloroaluminate,1-butyl-3-methylimidazolium tetrachloroborate,1-butyl-3-methylimidazolium thiocyanate, 1-dodecyl-3-methylimidazoliumiodide, 1-ethyl-2,3-dimethylimidazolium chloride,1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazoliumchloride, 1-ethyl-3-methylimidazolium hexafluorophosphate,1-ethyl-3-methylimidazolium tetrafluoroborate,1-hexyl-3-methylimidazolium tetrafluoroborate, 1-butyl-4-methylpyridiumchloride, 1-butyl-4-methylpyridium tetrafluoroborate,1-butyl-4-methylpyridium hexafluorophosphate,benzyldimethyltetradecylammonium chloride, tetraheptylammonium chloride,tetrakis(decyl)ammonium bromide, tributylmethylammonium chloride,tetrahexylammonium iodide, tetrabutylphosphonium chloride,tetrabutylphosphonium tetrafluoroborate, triisobutylmethylphosphoniumtosylate 1-butyl-1-methylpyrrolidinium,1-butyl-1-methyl-methylpyrrolidium bromide, 1-butyl-1-methylpyrrolidiumtetrafluoroborate, 1-aryl-3-methylimidazolium bromide,1-aryl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazoliumhexafluorophosphate, 1-benzyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium dibutylphosphate, 1-(3-cyanopropyl)-3-methylimidazoliumbis(trifluoromethylsulfonyl)amide, 1,3-dimethylimidazolium dimethylphosphate, 1-ethyl-2,3-dimethylimidazolium ethyl sulfate, and the like,preferably 1-ethyl-3-methylimidazolium aluminum chloride,1-butyl-4-methylpyridium hexafluorophosphate,benzyldimethyltetradecylaluminum chloride, tributylmethylaluminumchloride, tetrabutylphosphonium tetrafluoroborate,1-butyl-1-methylpyrrolidium chloride, 1-butyl-3-methylimidazoliumtetrachloroaluminate, 1-butyl-4-methylpyridium chloride,1-butyl-4-methylpyridium tetrafluoroborate, and the like.

The inorganic or organic porous carrier being treated by the ioniccompound has the —OH group remaining on the surface in the range of0.001 to 100 mmol per 1 g of the carrier before treating.

The carrier treated by the ionic compound may the inorganics or organicsand these should have the pore and the surface area which can supportthe ionic compound, metallocene, co-catalyst. The surface of the carrierhas the hydrophobic functional group, or may be used by surface-treatingwith several silane-based compound, the aluminum-based compound, thehalogen-based compound. The inorganic carrier that may be generally usedincludes the carriers being used in the supporting the existingmetallocene catalyst such as silica, alumina, magnesium chloride,magnesium oxide, and the like, in addition, the materials such asmesoporous material, MCM-41, CMC-48, SBA-15, and the like may be used,and these have the surface area of more than 100 m²/g and the porevolume of more than 0.1 cc/g. The clay compound such as mineral clay,kaolin, talc, mica, montmorillonite, and the like may be used as thecarrier. The material such as a polysiloxane-based polymer compound,polystyrene gel or bid, and the like may be adopted as an organiccarrier. Those supported compounds may be used in the originalcondition, and may be used by controlling the amount of the hydrophobicfunctional group, etc. in the surface of the carrier pore byheat-treating at the temperature of 100 to 1000° C.

A composition of the ionic compound being supported on the surface ofthe carrier is related to the physicochemical property of the carriersurface such as the pore surface area of the carrier and the amount ofthe hydroxy group (OH group) on the carrier surface, however the ioniccompound being mixed and contacted is suitably 0.001 to 50% by weightbased on the treated support, particularly 0.1 to 40% by weight ispreferred. In addition, the more the amount of the hydroxy groupremaining on the surface of the carrier, the amount of the ioniccompound should be increased. In case of less than 0.001% by weight ofthe ionic compound, the treating effect is insignificant, and in case ofover than 50% by weight, there is no synergy effect as much as theexcess amount, the waste of the ionic compound is caused.

In addition, the example of the metallocene or non-metallocene catalystthat may be used in the present invention is as follows, however it isnot necessarily limited thereto.

Cp′ among the transition metal represented by Chemical Formula 1 beingsupported to the inorganic or organic porous carrier being treated withthe ionic compound is the fused ring including the cyclopentadiene orcyclopentadienyl ring being able to η⁵-bond with central metal, isselected from the group consisting of cyclopentadienyl,methylcyclopentadienyl, dimethylcyclopentadienyl,tetramethylcyclopentadienyl, pentamethylcyclopentadienyl,butylcyclopentadienyl, sec-butylcyclopentadienyl,tert-butylmethylcyclopentadienyl, trimethylsillylcyclopentadienyl,indenyl, methylindenyl, ethylindenyl, isopropylindenyl, florenyl,methylflorenyl, dimethylflorenyl and ethylflorenyl, isopropylflorenyl,and the concrete example of the compound of Chemical Formula 1 includesbis(cyclopentadienyl)zirconium dichloride,bis(methylcyclopentadienyl)zirconium dichloride,bis(normalbutylcyclopentadienyl)zirconium dichloride,bis(cyclopentylcyclopentadienyl)zirconium dichloride,bis(cyclohexylcyclopentadienyl)zirconium dichloride,bis(1,3-dimethylcyclopentadienyl)zirconium dichloride,bis(isobutylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconiumdichloride, bis(florenyl)zirconium dichloride,bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride,ethylene-bis(indenyl)zirconium dichloride,ethylene-[bis(4,5,6,7-tetrahydro-1-indenyl)]zirconium dichloride,dimethylsillyl-bis(indenyl)zirconium dichloride,diphenylsillyl-bis(indenyl)zirconium dichloride,isopropyl(cyclopentadienyl)(florenyl)zirconium dichloride,dimethylsillyl(cyclopentadienyl)(florenyl)zirconium dichloride,diphenylsillyl(cyclopentadienyl)(florenyl)zirconium dichloride,(cyclopentylcyclopentadienyl)(cyclopentadienyl)zirconium dichloride,(1-methyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl)zirconiumdichloride, (1-ethyl-3-cyclopentylcyclopentadienyl)(cyclopentadienyl)zirconium dichloride,(1-butyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl)zirconiumdichloride, (cyclopentylcyclopentadienyl) (cyclomethylcyclopentadienyl)zirconium dichloride, (1-methyl-3-cyclopentylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,(1-ethyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl)zirconium dichloride, (1-butyl-3-cyclopentylcyclopentadienyl)(pentamethylcyclopentadienyl) zirconium dichloride,(cyclohexylcyclopentadienyl)(cyclopentadienyl)zirconium dichloride,(1-methyl-3-cyclohexylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,(1-ethyl-3-cyclohexylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride, (1-butyl-3-cyclohexylcyclopentadienyl)(pentamethylcyclopentadienyl) zirconium dichloride,(cyclohyxylmethyllenylcyclopentadienyl)(cyclopentadienyl)zirco niumdichloride, (cycloheptylcyclopentadienyl) (cyclopentadienyl)zirconiumdichloride,(1-methyl-3-cycloheptylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride, (1-ethyl-3-cycloheptylcyclopentadienyl)(pentamethylcyclopentadienyl) zirconium dichloride,(1-butyl-3-cycloheptylcyclopentadienyl) (pentamethylcyclopentadienyl)zirconium dichloride, (cyclohexylethyllenylcyclopentadienyl)(cyclopentadienyl) zirconium dichloride, and the like, in addition, themetallocene compound and non-metallocene compound that the central metalincludes titanium and hafnium transition metal may be used.

In case of the metallocene supported catalyst composition according tothe present invention, the supported metallocene or non-metalloceneorganic metal catalyst (the transition metal compound of ChemicalFormula 1) is suitably 0.01 to 10% by weight, and preferably 0.1 to 5%by weight based on the metallocene supported catalyst being supported inthe carrier being surface-treated with the ionic compound (based on thefinal supported catalyst including the carrier, the ionic liquid, theorganic metal catalyst, co-catalyst, and the like).

The metallocene supported catalyst composition according to the presentinvention further includes alkylaluminoxane co-catalyst, organicaluminum co-catalyst or boron compound co-catalyst, or the mixturethereof.

As the aluminoxane compound being used in the present invention, thealuminoxane represented by following Chemical Formula 3 is mainly used.

(—Al(R⁴)—O—)_(m)  [Chemical Formula 3]

where,

R⁴ is (C1-C20) alkyl group, preferably methyl group or isobutyl group,

m is an integer more than 5.

The example of the aluminoxane compound includes concretelymethylaluminoxane, ethylaluminoxane, propylaluminoxane,butylaluminoxane, isobutylaluminoxane, and the like.

Further, the alkyl compound co-catalyst being used in the presentinvention further includes the organic alkyl compound represented byChemical Formula 4.

(R⁵)_(r)Al(E)_(3-r)  [Chemical Formula 4]

where,

R⁵ is (C1-C8) alkyl group,

E is hydrogen atom or halogen atom,

r is an integer of 1 to 3.

The example of alkylaluminum compound includes trialkyl aluminumincluding trimethylaluminum, triethylaluminum, tripropylaluminum,triisopropylaluminum, tributylaluminum, triisobutylaluminum,triisorenylaluminum, and the like, dialkylaluminum chloride includingdimethylaluminum chloride, diethylaluminum chloride, dipropylaluminumchloride, diisobutylaluminum chloride and dihexylaluminumchloride,alkylaluminum dichloride including methylaluminum dichloride,ethylaluminum dichloride, propylaluminum chloride, isobutylaluminumchloride, and the like and preferably trialkylaluminum chloride,triisobutylaluminum chloride.

In addition, the boron compound that may be used as the co-catalyst inthe present invention may be selected from the compounds represented byfollowing Chemical Formulas 5 to 7.

B(R⁶)₃  [Chemical Formula 5]

[R⁷]⁺[B(R⁶)₄]⁻  [Chemical Formula 6]

[(R⁸)_(q)ZH]⁺[B(R⁶)₄]⁻  [Chemical Formula 7]

where,

B is a boron atom;

R⁶ is phenyl group, or fluorine atom or phenyl group having 3 to 5 ofsubstituents selected from (C1-C4)alkyl group or (C1-C4)alkoxy groupsubstituted with fluorine atom or unsubstituted;

R⁷ is cyclic (C5-C7) aromatic cation or alkyl substituted cation, forexample triphenylmethyl cation;

Z is nitrogen or phosphor atom;

R⁸ is (C1-C4) alkylradical or anylinium radical substituted with two(C1-C4) alkyl group together with nitrogen atom;

q is an integer of 2 or 3.

The example of the boron compound co-catalyst includes preferablytris(pentafluorophenyl) borane, tris(2,3,5,6-tetrafluorophenyl) borane,tris(2,3,4,5-tetrafluorophenyl) borane, phenylbis(pentafluorophenyl)borane, tetrakis(pentafluorophenyl) borate,tetrakis(2,3,5,6-tetrafluorophenyl) borate,tetrakis(2,3,4,5-tetrafluorophenyl) borate,tetrakis(3,4,5-tetrafluorophenyl) borate,tetrakis(2,2,4-trifluorophenyl) borate, phenylbis(pentafluorophenyl)borate or tetrakis(3,5-bistrifluoromethylphenyl) borate.

In addition, in case of aluminum-based co-catalyst such asmethylaluminoxane or alkylaluminum compound and boron-based co-catalystbeing applied, it is suitably 0.01 to 50% by weight, preferably 0.1 to30% by weight based on the metallocene supported catalyst beingsupported in the carrier being surface-treated with the ionic compound(the final supported catalyst).

In case of supporting in the carrier being surface-treated with theionic compound by dissolving the transition metal compound of ChemicalFormula 1 in the organic solvent like methylaluminoxane, the molar ratioof two components such as metallocene and co-catalyst in the finalsupported catalyst is suitably 1:0.01 to 1:1000, particularly 1:1 to1:500, based on the molar ratio of the transition metal:aluminum.

In case of using the boron compound as co-catalyst, the molar ratio ofthe transition metal compound of Chemical Formula 1: the boron compoundco-catalyst is suitably 1:0.01 to 1:100, particularly 1:0.1 to 1:20,based on the molar ratio of the transition metal:aluminum. In addition,the molar ratio of the boron compound co-catalyst and aluminum compoundis suitably 1:0.1 to 1:100, preferably 1:1 to 1:20, based on theboron:aluminum.

The present invention is characterized in the process for preparingolefin polymer by using the metallocene supported catalyst compositionfor the olefin polymerization, the olefin polymer includes homopolymeror copolymer of alphaolefin.

The example of the olefin-based monomer being able to adopt in thepresent invention includes ethylene, alphaolefin, cycloolefin, and thelike, dien-based monomer, trine-based olefine, styrene-based olefin andcyclic olefin.

The example of the monomer includes ethylene, propylene, 1-butene,1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, 1-eicocene, 4-methyl-1-pentene,3-methyl-1-pentene and 3-methyl-1-butene, styrene, par-methylstyrene,allylbenzene, divinylbenzene, vinylcyclohexane, vinylcycloheptane,cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene,1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene, cyclopentadiene, and it ispossible to polymerize by mixing the monomers with alone or two or more.

Hereinafter, the method for preparing the metallocene supported catalystcomposition according to the present invention will be described.

The inorganic or organic porous carrier being treated with the ioniccompound that the transition metal compound is supported, may beprepared from the following method:

-   -   a) mixing, bringing the ionic compounds alone, into contact with        a carrier without solvent, or    -   b) mixing the carrier and the ionic compound among the aliphatic        or aromatic hydrocarbon solvent to prepare the slurry, isolating        and drying the slurry to flow the inert gas such as nitrogen,        argon between 100 to 900° C. or treat through the vacuum in        order to control the amount of hydroxy group on the surface of        the inorganic carrier such as silica being used in the        treat-supporting by drying, correspondencing to the supporting        purpose.

In this case, the amount of the hydroxy group remaining on surface issuitably 0.001 to 100 mmol-OH/g-silica, preferably 0.1 to 5mmol-OH/g-silica. The above requirement is the requirement for thecarrier before being treated with the ionic compound, the ionic compoundis added at needs to the flask of the silica being prepared in thecarrier, when adding it is fine to add with the organic solvent. Theamount of the adding ionic compound is similar to the amount of OH groupon the silica surface or is more than those.

The silica, ionic compound are sufficiently mixed for more than one hourunder the nitrogen atmosphere at the temperature of more than themelting point of the ionic compound, to contact the ionic compound withthe silica surface and the hydroxy group on the silica surface. In caseof using the organic solvent, the organic solvent is removed aftertreating the surface, and then the next step is proceeded. Themetallocene compound and co-catalyst methylaluminoxane(MAO) aredissolved to the organic solvent such as toluene in the another flask,and the molar ratio of the metallocene and aluminum of the co-catalystis suitably 1:0.1 to 1:3000, and preferably 1:1 to 1:500 based on thetransition metal:aluminum. The metallocene solution is added to thesilica being surface-treated with the ionic compound, and stirred underthe nitrogen atmosphere at the suitable temperature for the suitabletime, to support the metallocene and the co-catalyst. Then, in order toremove the unsupported metallocene and co-catalyst, after washing morethan three times by using the organic solvent such as toluene, etc., anddrying with the vacuum or nitrogen gas, etc., finally the metallocenecatalyst being supported in the carrier being surface-treated with theionic compound is obtained.

Another method for preparing of the metallocene supported catalyst willbe described as follows. After the heat-treated silica issurface-treated as above by using the ionic compound, the metallocenecompound is added to the surface-treated silica by dissolving alone tothe organic solvent such as toluene, and stirred at the suitabletemperature for the suitable time, under the nitrogen atmosphere tosupport the metallocene compound. Then, in order to remove theunsupported metallocene, after washing more than three times by usingthe organic solvent such as toluene, etc., and drying with the vacuum ornitrogen gas, etc., finally the metallocene catalyst being supported inthe carrier being surface-treated with the ionic compound is obtained.The catalyst being supported with the metallocene alone in the carrierbeing surface-treated with the obtained supported ionic compound may beused by adding the co-catalyst necessary to the polymerization of thepolymer such as polyolefin, etc. to the polymerization solvent, etc.

Another method for preparing the metallocene supported catalyst of thepresent invention will be described as follows.

After the heat-treated silica is surface-treated as above by using theionic compound, MAO or the borate-based co-catalyst is added to thesurface-treated silica by dissolving to the organic solvent such astoluene, and mixed at the suitable temperature for the suitable time,under the nitrogen atmosphere to support. Then, in order to remove theunsupported MAO, after washing more than three times by using theorganic solvent such as toluene, etc., and drying with the vacuum ornitrogen gas, etc., finally the carrier being surface-treated with theionic compound and co-catalyst is obtained. The metallocene is supportedto the silica being supported co-catalyst on the ionic compound bydissolving metallocene compound to the organic solvent such as toluene,adding them to the surface-treated silica and stirring at the suitabletemperature for the suitable time, under the nitrogen atmosphere. Then,in order to remove the unsupported metallocene compound, after washingmore than three times by using the organic solvent such as toluene,etc., and drying with the vacuum or nitrogen gas, etc., finally themetallocene catalyst being supported to the carrier beingsurface-treated with the ionic compound is obtained.

Another method for preparing the metallocene supported catalyst of thepresent invention will be described as follows.

After the heat-treated silica is surface-treated as above by using theionic compound, the metallocene compound and co-catalyst of theco-catalyst boron compound, co-catalyst of aluminum alkyl based aredissolved to the organic solvent such as toluene in the another flask,and the molar ratio of the metallocene and boron of the co-catalyst issuitably 1:0.1 to 1:100, and preferably 1:0.5 to 1:30. In addition, themolar ratio of the metallocene and aluminum alkyl compound is suitably1:0.1 to 1:100.

The metallocene compound and borate-based co-catalyst solution are addedto the silica being surface-treated with the ionic compound, stirred andmixed under nitrogen atmosphere at the suitable temperature for thesuitable time to support the metallocene compound and co-catalyst. Then,in order to remove the unsupported metallocene compound and co-catalyst,after washing more than three times by using the organic solvent such astoluene, etc., and drying with the vacuum or nitrogen gas, etc., finallythe metallocene catalyst being supported in the carrier beingsurface-treated with the ionic compound is obtained.

The amount of the transition metal in the supported catalyst beingprepared by the above method is analyzed as 0.05 to 1.5% by weight.

The metallocene supported catalyst being supported in the above obtainedionic compound is able to multiple polymerization by using one type ofolefin monomer or more than two types of these monomers, and thepolymerization of the olefin monomer is carried out on the slurry of theorganic solvent such as hexane, etc. or the vapor phase. The catalystaccording to the present invention is used by dispersing in the reactionsolvent under the condition of no water, as the polymerization reactionsolvent, generally the aliphatic hydrocarbon or the mixture thereof isused and is for example, propane, isobutane, isopentane, hexane,heptane, octane, etc.

The metallocene supported catalyst of the present invention is able toapply to the vapor phase, the slurry, the liquid polymerization processas well as batch, continuous polymerization process, but is mostsuitable for the slurry and the vapor phase reaction.

The batch slurry polymerization process as the example of the polyolefinpolymerization method by using the supported catalyst according to thepresent invention is described as follows.

First of all, the water and air in the high-pressure reactor are removedwith the vacuum at high temperature, the solvent is added to thereactor, the temperature is increased to the polymerization temperature,then the alkylaluminum or MAO is added as a scavenger, and themetallocene supported catalyst according to the present invention isadded. Then, the olefin such as ethylene, etc. is added, the hydrogen isadded together with adding of the olefin as necessary. If it is reachedto the required polymerization time, the adding of the olefin isstopped, the unreacted olefin and the solvent are removed, and thereactor is opened to yield the polymer in the condition of solid.

The used polymerization solvent may be used after passing through thetube being filled with the molecular sieve 5A and the activated aluminaand sufficiently removing the water, oxygen and other catalytic poisonby bubbling with the high purity of nitrogen, the polymerizationtemperature is −50 to 200° C., and suitably 50 to 100° C. Thepolymerization pressure is 1 to 50 atm, and preferably 5 to 30 atm.

ADVANTAGEOUS EFFECTS

The metallocene supported catalyst being supported to the carrier beingsurface-treated with the ionic compound according to the presentinvention has very excellent catalysis activity and good bulk density ofthe produced polymer compared to the existing general supporting method.Therefore, it is very economical and useful to produce the metallocenepolyolefin in the commercial slurry or vapor phase process.

BEST MODE

Hereinafter, the embodiments of the present invention will be describedin detail with reference to the compared example and example, but thepresent invention is not limited to the following example.

The metallocene supported catalyst and polymer analysis according to thepresent invention was carried out with following method.

-   -   1) The amount of the metal among the supported catalyst        -   The amount of the metal was measured by ICP (Inductively            Coupled Plasma Spectroscopy) analysis and by the following            analysis by using IPC analysis apparatus (Perkin Elmer,            Optima 200DV).    -   Analysis        -   The supported catalyst of 60 mg in the glove box was added            to the vial having the magnetic bar.        -   To the vial being added the supported catalyst, 12 ml nitric            acid was added and sufficiently stirred for one hour.        -   After one hour, the nitric acid mixture solution was            filtered through a filter paper and 1 ml solution was put to            the new vial.        -   After preparing the 10 times diluted solution by putting 9            ml the distilled water to the new vial, the diluted solution            was analyzed ICP.    -   2) Melt Index        -   The melt index was measured on the basis of ASTM D2839.    -   3) Melting Point Analysis        -   This was measured under the condition of 2^(nd) heating at            the speed of 20° C./min. under the nitrogen atmosphere by            using Dupont DSC2910.    -   4) Molecular Weight and Molecular Weight Distribution        -   This was measured at the speed of 1 ml/min. at the            temperature of 160° C. by using PL GPC210 (Product made by            Polymer Laboratories Company) equipped with Column TSK Guard            Column HHR(S)+TSK-Gel GMHHR H(S) being made by TOHO Company.            1,2,3-trichlorobenzene was used as the solvent, and the            molecular weight was calibrated with standard sample            PS1_A,B(Mw=580˜7,500,000).

Example 1 1. Preparation of the Metallocene Supported Catalyst to theSilica being Surface-Treated with the Ionic Compound

To the round-bottom flask equipped with a stopcock, 1 g of silicaXPO-2412 (U.S., Grace Company, surface area 460 m²/g, average porediameter 12.8 mm) was added, 1-butyl-3-methylimidazolium tetrachloroaluminate of 308 mg (1.0 mmol) was added as the ionic compound andsufficiently stirred at 70° C. for 3 hours by using magnetic bar tosurface-treat with the ionic compound, and 30 ml toluene was added. Tothe round-bottom flask equipped with another stopcock, 0.35 mmol(n-BuCp)₂ZrCl₂ and 8 mmol-Al MAO solution being diluted in toluene(aluminum content 4.6% by weight, Albermale Company) was added andstirred at room temperature for 30 min. The metallocene, co-catalystsolution was moved to the surface-treated with the above ionic solution,and was stirred at 70° C. for three hours to support the metallocene andMAO. After stopping the stirring and sinking silica, upper solution wasremoved out, 50 ml toluene was added and stirred for 10 min. The sameprocedure was repeated three times and washed. Then, The remainingtoluene in the flask for one hour was removed with vacuum to yield themetallocene supported catalyst of 1.58 g.

2. Polymerization of Ethylene Slurry

After 1.5 liter hexane was added to the 2 liter high-pressure reactorbeing washed at high temperature and vacuum, the temperature wasincreased to 70° C., 2 mmol-Al MAO was added for the role of scavengerand co-catalyst, and the above prepared metallocene supported catalystof 8 mg was added to the reactor as the hexane slurry. After theethylene pressure was controlled to be 7 atm of the total pressure inthe reactor, the ethylene gas was added and was saturated, the ethylenepolymerization reaction was started by rotating the stirrer. Totalpolymerization reaction time was 60 min. and the temperature wasmaintained at about 70° C. After the reaction was finished, the preparedpolymer was washed with ethanol and was dried under vacuum to yield thepolymer of about 25 g.

Example 2 1. Preparation of the Metallocene Supported Catalyst to theSurface-Treated Silica with the Ionic Compound

The catalyst was prepared according to the procedure for preparing themetallocene supported catalyst of Example 1-1, except that1-butyl-3-methylimidazolium tetrachloroaluminate of 150 mg was used asthe ionic compound to treat surface of silica and the metallocenecompound [(n-BuCp)₂ZrCl₂] was supported, the yielded supported catalystwas 1.42 g.

2. Polymerization of Ethylene Slurry

The polymerization reaction was carried out according to thepolymerization method of ethylene slurry in 2 of [Example 1] by usingthe above prepared supported catalyst, to yield the polymer of about 43g.

Example 3 1. Preparation of the Metallocene Supported Catalyst to theSurface-Treated Silica with the Ionic Compound

The catalyst was prepared according to the procedure for preparing themetallocene supported catalyst of Example 1-1, except that1-butyl-3-methylpyridinium hexafluorophosphate of 150 mg was used as theionic compound to treat surface of silica and the metallocene compound[(n-BuCp)₂ZrCl₂] was supported, the yielded supported catalyst was 1.44g.

2. Polymerization of Ethylene Slurry

The polymerization reaction was carried out according to thepolymerization method of ethylene slurry in 2 of [Example 1] by usingthe above prepared supported catalyst, to yield the polymer of about 42g.

Example 4 1. Preparation of the Metallocene Supported Catalyst to theSurface-Treated Silica with the Ionic Compound

The catalyst was prepared according to the procedure for preparing themetallocene supported catalyst of Example 1-1, except that1-butyl-3-methylpyridinium tetrafluoroborate of 240 mg was used as theionic compound to treat surface of silica and the metallocene compound[(n-BuCp)₂ZrCl₂] was supported, the yielded supported catalyst was 1.50g.

2. Polymerization of Ethylene Slurry

The polymerization reaction was carried out according to thepolymerization method of ethylene slurry in 2 of [Example 1] by usingthe above prepared supported catalyst, to yield the polymer of about 40g.

Example 5 1. Preparation of the Metallocene Supported Catalyst to theSilica being Surface-Treated with the Ionic Compound

To the round-bottom flask equipped with a stopcock, 1 g of silicaXPO-2412 (U.S., Grace Company) was added, 1-butyl-3-methylpyridiniumchloride of 95 mg was added as the ionic compound and sufficientlystirred at 170° C. for three hours by using a magnetic bar tosurface-treat with the ionic compound, the temperature was decreased to70° C. and 30 ml toluene was added. To the round-bottom flask equippedwith another stopcock, 0.35 mmol (n-BuCp)₂ZrCl₂ and 8 mmol-Al MAOsolution being diluted in toluene (aluminum content 4.6% by weight,Albermale Company) were added and stirred at room temperature for 30min. The metallocene, co-catalyst solution were moved to thesurface-treated with the above ionic solution, and was stirred at 70° C.for three hours to support the metallocene and MAO. After stopping thestirring and sinking silica, upper solution was removed out, 50 mltoluene was added and stirred for 10 min. The same procedure wasrepeated three times and washed. Then, the toluene remaining in theflask was removed with vacuum for one hour to yield the finalmetallocene supported catalyst of 1.28 g.

2. Polymerization of Ethylene Slurry

The polymerization reaction was carried out according to thepolymerization method of ethylene slurry in 2 of [Example 1] by usingthe above prepared supported catalyst, to yield the polymer of about 106g.

Example 6 1. Preparation of the Metallocene Supported Catalyst to theSurface-Treated Silica with the Ionic Compound

The catalyst was prepared according to the procedure for preparing themetallocene supported catalyst of Example 5-1, except that1-butyl-3-methylpyridinium chloride of 290 mg was used as the ioniccompound to treat surface of silica, the yielded supported catalyst was1.25 g.

2. Polymerization of Ethylene Slurry

The polymerization reaction was carried out according to thepolymerization method of ethylene slurry in 2 of [Example 1] by usingthe above prepared supported catalyst, to yield the polymer of about 75g.

Example 7 1. Preparation of the Metallocene Supported Catalyst to theSilica being Surface-Treated with the Ionic Compound

To the round-bottom flask equipped with a stopcock, 1 g of silicaXPO-2412 (U.S., Grace Company) was added, 1-butyl-3-methylpyridiniumchloride of 290 mg was added as the ionic compound and sufficientlystirred at 170° C. for three hours by using a magnetic bar tosurface-treat with the ionic compound, the temperature was decreased to70° C. and 15 ml toluene was added. To the round-bottom flask equippedwith another stopcock, 0.35 mmol (n-BuCp)₂ZrCl₂, 0.42 mmoltriphenylcarboniumpentafluorophenylborate, 0.7 mmol triethylaluminium,and 20 ml toluene were added and stirred at room temperature for 30 min.The metallocene compound, co-catalyst solution were moved to thesurface-treated with the above ionic solution, and was stirred at 70° C.for two hours to support the metallocene compound and the boratecompound. After stopping the stirring and sinking silica, upper solutionwas removed out, 50 ml toluene was added and stirred for 10 min. Thesame procedure was repeated three times and washed. Then, the tolueneremaining in the flask for 1 hour was removed with vacuum to yield thefinal metallocene supported catalyst of 1.54 g.

2. Polymerization of Ethylene Slurry

The polymerization reaction was carried out according to thepolymerization method of ethylene slurry in 2 of [Example 1] by usingthe above prepared supported catalyst, to yield the polymer of about 30g.

Comparative Example 1 1. Preparation of the Metallocene SupportedCatalyst

To the round-bottom flask equipped with a stopcock, 1 g of silicaXPO-2412 was added and 30 ml toluene was added. To the round-bottomflask equipped with another stopcock, 8 mmol-Al MAO and 0.35 mmol(n-BuCp)₂ZrCl₂ in toluene solution were added and stirred for 30 min.The above mixed solution was moved to the flask containing the preparedsilica and stirred at 50° C. for one hour. After stopping the stirringand sinking silica, upper solution was removed out, 50 ml toluene wasadded and stirred for 10 min. The same procedure was repeated threetimes. Then, the toluene remaining in the flask was removed with vacuumfor one hour to yield the metallocene supported catalyst of 1.10 g.

2. Polymerization of Ethylene Slurry

The polymerization reaction was carried out according to thepolymerization method of ethylene slurry in 2 of [Example 1] by usingthe above prepared supported catalyst, to yield the polymer of about 41g.

Comparative Example 2 1. Preparation of the Metallocene SupportedCatalyst

To the round-bottom flask equipped with a stopcock, 1 g of silicaXPO-2412 was added. To the round-bottom flask equipped with anotherstopcock, 3 mmol-Al MAO and 0.35 mmol (n-BuCp)₂ZrCl₂ in toluene solutionwere added and stirred for 30 min. The above mixed solution was moved tothe flask containing the prepared silica and stirred at 50° C. for onehour. After stopping the stirring, the remaining toluene in the flaskwas removed with vacuum for one hour to yield the metallocene supportedcatalyst of 0.98 g.

2. Polymerization of Ethylene Slurry

The polymerization reaction was carried out according to thepolymerization method of ethylene slurry in 2 of [Example 1] by usingthe above prepared supported catalyst, to yield the polymer of about 11g.

TABLE 3 Catalyst Synthesis Table Ionic Ionic compound compound Supportedtreating amount of metallocene Supported Ionic compound temperatureadding compound co-catalyst Example 1 1-butyl-3- 70 1.0 (n- MAOmethylimidazolium BuCp)₂ZrCl₂ tetrachloroaluminate Example 2 1-butyl-3-70 0.5 MAO methylimidazolium tetrachloroaluminate Example 3 1-butly-4-70 0.5 (n- MAO methylpyridinium BuCp)₂ZrCl₂ hexafluorophosphate Example4 1-butyl-4- 70 1.0 (n- MAO methylpyridinium BuCp)₂ZrCl₂tetrafluoroborate Example 5 1-butyl-4- 170 0.5 (n- MAO methylpyridiniumBuCp)₂ZrCl₂ chloride Example 6 1-butyl-4- 170 1.5 (n- MAOmethylpyridinium BuCp)₂ZrCl₂ chloride Example 7 1-butyl-4- 170 1.5 (n-Ph3C—B(C6F5)4 methylpyridinium BuCp)₂ZrCl₂ chloride Comparative — — —(n- MAO Example 1 BuCp)₂ZrCl₂ Comparative — — — (n- MAO Example 2BuCp)₂ZrCl₂ * Ph3C—B(C6F5)4: triphenylcarboniumpentafluorophenyl boron

TABLE 4 Polymerization Requirements and Results Co-catalyst Amount of PEwhen catalyst Yield GPC DSC Apparent polymerizing Solvent (mg) (g)Activity MI MWD (° C.) Density Example 1 MAO n- 8 25 3.1 Measurement —136 0.30 hexane imposible Example 2 MAO n- 7 43 6.2 Measurement — 1380.29 hexane impossible Example 3 MAO n- 7 42 6.0 Measurement — 136 0.29hexane impossible Example 4 MAO n- 9 40 4.5 0.005 2.8 137 0.28 hexaneExample 5 MAO n- 11 106 9.7 0.008 2.4 135 0.30 hexane Example 6 MAO n-10 75 7.5 0.001 2.3 135 0.31 hexane Example 7 MAO n- 12 30 2.5 0.002 2.4132 0.32 hexane Comparative MAO n- 10 41 4.1 0.06 2.3 138 0.30 Example 1hexane Comparative TEAL n- 15 11 0.7 0.24 2.3 140 0.32 Example 2 hexane*activity: kg-PE/g-cat., hr, 7 bar *M.I: g/10 min. *polymerizationpressure and time: 6~7 bar, 60 min.

1. A metallocene supported catalyst composition for polymerizing olefinbeing prepared by supporting the group IV transition metal compoundrepresented by following Chemical Formula 1 to the inorganic or organicporous carrier being treated with the ionic compound:Cp′L¹ML² _(n)  [Chemical Formula 1] where, M is Group IV transitionmetal of the Periodic Table of the elements; Cp′ is the fused ringincluding the cyclopentadiene or cyclopentadienyl ring being able toη⁵-bond with central metal; L¹ is the fused ring includingcyclopentadiene, cyclopentadienyl ring or an anionic ligand including(C1-C20) hydrocarbon substituent and O, N or P atom; L² is halogen atom,(C1-C20) alkyl group, (C6-C30) aryl (C1-C20) alkyl group, (C3-C20)cycloalkyl group, (C1-C20) alkoxy group, (C6-C30) aryloxy group,(C6-C30) aryl group, (C1-C20) alkyl substituted or (C6-C30) arylsubstituted sillyl group, (C1-C20) alkyl substituted or (C6-C30) arylsubstituted amino group, (C1-C20) alkyl substituted or (C6-C20) arylsubstituted syloxy group, and (C1-C20) alkyl substituted or (C6-C30)aryl substituted phosphine group; n is an integer of 1 or 2; Cp′ and L¹may be not connected each other, or may be connected to a silicon or(C1-C4) alkenylene bond; the cyclopentadienyl ring or cyclopentadienylfused ring of the Cp′ and L¹ may be further substituted with (C1-C20)alkyl group, (C6-C30) aryl group, (C2-C20) alkenyl group or (C6-C30)aryl (C1-C20) alkyl group.
 2. The metallocene supported catalystcomposition for polymerizing olefin of claim 1, wherein the ioniccompound has the polarity in the liquid or solid phase at thetemperature range of −100 to 300° C.
 3. The metallocene supportedcatalyst composition for polymerizing olefin of claim 1, wherein theionic compound is selected from the compound of following ChemicalFormula 2 and the mixture thereof:X⁺Y⁻  [Chemical Formula 2] where, X⁺ is imidazolium ion, pyridium ion,ammonium ion, phosphonium ion, sulfonium ion, pyrazolium ion orpyrrolidium ion; Y⁻ is BF₄ ⁻, PF₆ ⁻, AlCl₄ ⁻, halogen⁻, CH₃CO₂ ⁻, CF₃CO₂⁻, CH₃SO₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)N⁻, NO₃ ⁻, SbF₆ ⁻, Sb₂F11⁻, MePhSO₃ ⁻,(CF₃SO₂)₂N⁻, (CF₃SO₂)₃C⁻ or (OR)₂PO₂ ⁻.
 4. The metallocene supportedcatalyst composition for polymerizing olefin of claim 3, wherein theionic compound of the Chemical Formula 2 is selected from the1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazoliumdibutylphosphate, 1-butyl-3-methylimidazolium dicyanamide,1-butyl-3-methylimidazolium hexafluoroantimonate,1-butyl-3-methylimidazolium hexafluorophosphate,1-butyl-3-methylimidazolium hydrogencarbonate,1-butyl-3-methylimidazolium hydrogensulfate, 1-butyl-3-methylimidazoliummethylsulfate, 1-butyl-3-methylimidazolium tetrachloro aluminate,1-butyl-3-methylimidazolium tetrachloroborate,1-butyl-3-methylimidazolium thiocyanate, 1-dodecyl-3-methylimidazoliumiodide, 1-ethyl-2,3-dimethylimidazolium chloride,1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazoliumchloride, 1-ethyl-3-methylimidazolium hexafluorophosphate,1-ethyl-3-methylimidazolium tetrafluoroborate,1-hexyl-3-methylimidazolium tetrafluoroborate, 1-butyl-4-methylpyridiumchloride, 1-butyl-4-methylpyridium tetrafluoroborate,1-butyl-4-methylpyridium hexafluorophosphate,benzyldimethyltetradecylammonium chloride, tetraheptylammonium chloride,tetrakis(decyl)ammonium bromide, tributylmethylammonium chloride,tetrahexylammonium iodide, tetrabutylphosphonium chloride,tetrabutylphosphonium tetrafluoroborate, triisobutylmethylphosphoniumtosylate 1-butyl-1-methylpyrrolidinium,1-butyl-1-methyl-methylpyrrolidium bromide, 1-butyl-1-methylpyrrolidiumtetrafluoroborate, 1-aryl-3-methylimidazolium bromide,1-aryl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazoliumhexafluorophosphate, 1-benzyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium dibutylphosphate, 1-(3-cyanopropyl)-3-methylimidazoliumbis(trifluoromethylsulfonyl)amide, 1,3-dimethylimidazolium dimethylphosphate and 1-ethyl-2,3-dimethylimidazolium ethyl sulfate, or themixture thereof.
 5. The metallocene supported catalyst composition forpolymerizing olefin of claim 1, wherein the supported catalystcomposition further includes alkylaluminoxane co-catalyst, organicaluminum co-catalyst or boron compound co-catalyst or the mixturethereof.
 6. The metallocene supported catalyst composition forpolymerizing olefin of claim 5, wherein the alkyl aluminoxaneco-catalyst is selected from methylaluminoxane, ethylaluminoxane,propylaluminoxane, butyl aluminoxane and isobutyl aluminoxane compound;the organic alkyl aluminum co-catalyst is selected fromtrimethylaluminum, triethyl aluminum and diisobutylaluminum chloridecompound; the boron compound co-catalyst is selected from the groupconsisting of tris(pentafluorophenyl) borane,N,N-dimethylaniliumtetrakispentafluorophenylborate andtriphenylmethylliniumtetrapentakisfluoroborate.
 7. The metallocenesupported catalyst composition for polymerizing olefin of claim 1,wherein the Cp′ is selected from the group consisting ofcyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl,tetramethylcyclopentadienyl, pentamethylcyclopentadienyl,butylcyclopentadienyl, sec-butylcyclopentadienyl,tert-butylmethylcyclopentadienyl, trimethylsillylcyclopentadienyl,indenyl, methylindenyl, ethylindenyl, isopropylindenyl, fluorenyl,methylfluorenyl, dimethylfluorenyl and ethylfluorenyl,isopropylfluorenyl.
 8. The metallocene supported catalyst compositionfor polymerizing olefin of claim 1, wherein the inorganic or organicporous carrier being treated with the ionic compound is treated by: a)bringing the ionic compound alone into contact with a carrier withoutsolvent, or b) mixing the carrier and the ionic compound in thealiphatic or aromatic hydrocarbon solvent to obtain the slurry,isolating and drying the slurry.
 9. The metallocene supported catalystcomposition for polymerizing olefin of claim 1, wherein the ioniccompound is 0.001 to 50% by weight based on the treated support.
 10. Themetallocene supported catalyst composition for polymerizing olefin ofclaim 5, wherein the ratio of the supported transition metal compound ofChemical Formula 1: aluminoxane co-catalyst is 1:0.01 to 1:1000 based onthe molar ratio of the transition metal:aluminum.
 11. The metallocenesupported catalyst composition for polymerizing olefin of claim 5,wherein the ratio of the supported transition metal compound of ChemicalFormula 1: boron compound co-catalyst is 1:0.01 to 1:100 based on themolar ratio of the transition metal:boron.
 12. The metallocene supportedcatalyst composition for polymerizing olefin of claim 1, wherein thecarrier is selected from silica, alumina, magnesium chloride, magnesiumoxide, mineral clay, kaolin, talc, mica, montmorillonite,polysiloxane-based polymer compound and polystyrene, or the mixturethereof.
 13. A method for preparing the olefin polymer by using themetallocene supported catalyst composition for polymerizing olefin ofclaim
 1. 14. The method for preparing the olefin polymer of claim 13,wherein the olefin polymer is homopolymer or copolymer of alphaolefin.15. The method for preparing the olefin polymer of claim 14, wherein thealphaolefin is selected from ethylene, propylene, 1-butene, 1-pentene,1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene,3-methyl-1-pentene and 3-methyl-1-butene, or the mixture thereof.
 16. Anolefin polymer prepared by using the metallocene supported catalystcomposition for polymerizing olefin of claim 1.